Azodyestuffs



Patented Mar. 14, 1933 ST e -E F Q i IGQQfifiNE-ON-THE-RHINE, GERMANY,

os LEvEnKUsnN-r. G. WERE, Ann HEINRICH oninensrnm one ASSIGNORS TGENERAL Am -Jinn WORKS,

me, on NEW YORK, N. Y., A oonroaar on or DELAW RE" AzonYEsruFFs NoDrawing. Application filed March 2, 1932, Serial No. 596,404, and inGama Manna-1931..

The present invention relates to new azodyestuffs, more particularly itrelates to azodyestuffs which may be represented by the probable generalformula:

r l l (on): on), some (sols). N=N-R' ha e 1 stands for the carboxylicacid group or for an alkoxy group, R and R stands for radicals of thebenzene or naphthalene series,

thesubstituents a being attached to R or R' respectivelyinortho-position to the azo-group, each azo-group being attached to therespective hydroxy-naphthalene-sulfonic acid radical in ortho-positiontoa hydroxy group, and n and n' stand for thenum-Q bers one or two.

,Our new azodyestuiis are obtainable by tetrazotizing in the usualmanner one molecular proportion of a 4.4-diaminodiphenyl which issubstituted in the 3- and 8 position by carboxylic acid or alkoXy groupsor a corresponding lA!-diaminodiphenylurea compound, coupling in analkaline medium with two molecular proportions of a similar ordissimilar dihydroxynaphthalene-monoor -disulfonic acid and coupling thedisazodyestufl thus obtained with twomolecular proportions of a similaror dissimilar diazotized amine of the benzene or naphthaline seriescontaining in ortho-position to thediazotized amino group an alkoxy or;carboxy group. These o-alkoxy or o-carboxy amines of the benzene ornaphthalene series may be fur-- ther substituted in the nucleus,forexample pl'ex'compounds,lyielding shades of excellent ofgoodfastn'ess tolight and ironing.

group; 7

Our new dyestufis are inform of their all' kali metal salts [darkpowders," soluble in water, dyeing thevegetable"fibre'reddishtogreenish-grey shades. By after-treating the dyestuffs substance or onthe fibre with an agent yielding copperthey form copper com-.

fastness to light. f V a The invention is illustrated by the follow-.ing examples, without being limited thereto:

Ewmnple 1.244 parts by weight of 4.4

diamino-3.3 -dimethoxydiphenylare tetrazo tized and coupled with 672parts by weight of 1.S-dihydroXyhaphthalene-3.7-disulfonic acidl Theisolated dyestufi is dissolved in about 13,000 parts by weight of waterand coupled in an ice-cold soda alkaline solution with the diazocompound from 213 parts by weight of-2 amino-l anisol-4l-sulfonic acidin the presence of pyridine. When the diazo. compound can no more bedetected the tria) sa-zodyestufi thus-obtained is combined in the samemediumwith the diazo compound from 165.5 parts by weight of a -ohloroQamino-l-f 'anisol without isolation. The tetrakisazodye'stuflfpreicipitatingion the. addition 015 common salt is soluble in water witha green coloration and dyes cotton bluish-greenishrey" shades. ,By,after-treatment with copper sulfate 'yellowish greenish-grey shadesresult. i l i ,7

When coppering the dyestufl in substance by adding 26,000 parts byweight of water, while stirring, boiling the mixture for 2 hours in;anaqueous weakly'acid'solution from 750 parts by weight of crystallizedcopper sulfate and drying the isolated dyestufi thus obtained as sodiumsalt, cotton is dyedfrom an alkalinebath greenish-grey shades In itsfree state the dyestufi has the following formula:

dye-stuff of Example 2, which on after treatment with copper sulfatebecomes still more on 00113 00113 on l 70 n03s N= N=N N -S 03H 11038 a I75 OOH; H3OO "Emample 52. 244 parts by weight of 4.45 reddish. I v rdiamino-3.3-dimethoxydiphenyl are tetrazo- 'By dissolving the dyestuffin about 25,000 tized and coupled in a bicarbonate-alkaline parts byweight of water, acidifying the sosolution with 504 parts by weight of2.8-dilution, rendering the same ammoniacal,addhydroxynaphthalene:6-sulfonic acid, andthe ing. an' aqueous'aminoniacalsolution' pre- 85 isolated dyestuif is further coupled in anicepared from 800 parts by weight of crystalcold sodaalkalinesolutionwwith the diazo '(llZGCl copped sulfate'andheating for 2 hourscompound from 426 parts by weight-of 2- 'at 75 to 80 C. there is formeda complex amino l-anisoll-sulfonic acid,- while adding compound of thedyestuif which after isolapyridine. On the additioni'of commonisalt tionin the usual manner dyes cotton bluish-r 90 the dyestufi' .is isolatedandthen dried. It is grey shades of very good fastness to light.

, solubleinwater with aI dull bluish-yiolet'col- E wample 4.'302 partsby weight of 4.4- oration and dyes cotton bluish-grey shades,diamino-3.3-dimethoxydiphenylurea are tetewhich on.afteretreatmentwith.copper sulrazotized and coupled in a sodaalkaline solufate, become-morereddish. .lnitsfree state tion with 504 parts by weight of 2.5-dihy- 95the dyestuff possesses the following formula:droXynaphthalene-7-sulfonic acid. The dis- VSVOQH azodyestuff thusformed is isolated, again dis- 1 solved and coupled in a sodaalkalinesolution N: OH 00113 with a-diazo compound prepared from426 parts byweight of 2-amiI1o-1-aI1is0l-L-sul--;100

0 1 fonic acid. The tetrakisazodyestufi is isoj lated inthe usualmanner. In its free state 50H 2 it has the; probable formula Y I .405HO3SV 1- I=1-r When thedyestufi' is cop-pered-in substance, It dyescotton Violet-greyshades which by d rib d i Ex l 1, tt i d dafter-treatment with copper sulfate become grey shades of excellentfastness to light. Somewhat e E z 3 B b tit ti j E l The same dyestuffisobtalnable by dlazo- 2 the 2.8-dihydroxynaphthalene ti-sulfonic tlzlng 1me r PPQPQ Q of acid by the same quantity of g amlno-l-anlsol, couplingin an alkalmesolu- 55 naphthalene-'Y-sulfonic .acid, there is ob- Wlthmolecular propolitlon tained a dyestufi which in its free state hashydrixympllthalene761111501110 acld l th f 011 Owin g formula: lIlgWlthsodium sulfide to thecorresponding aminoazodyestufl'f, phosgenatlng thesame H.038 O and coupling withl molecular proportion of p l diazotized2-amino-1-anis0l-l-sulfonic acid. I scan on tons j Reducing andphosgenating may also be performed after the coupling with diazotized 2-Q amino-l-anisol l-sulfonic acid.

' v 2 When coppering the dyestufi in substance, 1 0 OH as described inExamp le 3, in an aminoniacal 5 It dyes cotton more reddishshades, thanthe solution, a copper complex compound of this dyestufi is obtainedwhich dyes cotton greyish-violet shades of very good fastness to light.g 7

By substituting the Q-amino-l-anisoll-sulfonic acid by thel-amino-2-naphtholmethyl (or ethyl) ether or a sulfonic acid thereof, adyestulf having similar properties is obtained.

Example 5.When coupling the dia-zo compound from 244: parts by weight of4.4- diamino-3.3-dimethoxydiphenyl with 504 parts by Weight of2.8-dihydroxynaphthalene-6-sulfonic acid as described in Example 2,combining this disazodyestulf with the diazo compound from 436 parts byvweight of 4-sulfonic acid-Q-aminobenzoic acid, coppering the dyestulf insubstance, as described in Example 1, or on the fibre grey shades areobtained which possess excellent fastness to light. In its free statethe dyestufl? has the probable formula:

A dyestut'f having similar properties is obtained by substituting the244 parts by weight of 4.4-cliamino-3.3-dimethoxydiphenyl by 272 partsby weight of Af-dr aminodiphenyl-3.3-dicarboxylic acid.

We claim: a

1. Azodyestufis of the probable general formula:

I wherein w stands for a carbon-carbon linkage or for the urea br1dge,ystands for the carboxylic acid group or for an alkoxy group, 2 standsfor the carboxylic acid group or for an alkoxy group, R and 3' standsfor radicals of the benzene or nathalene series, the substituents .2being at- 7 tionto a hydroxy group, and n and n ing attached to therespective hydroxy-naphthalene-sulfonic acid radical in ortho-posistandfor the numbers one or two, beingin form'of their alkali metal saltsdarkpowders, soluble in water, dyeing the vegetable fibre reddishtogreenish-grey shades, which by after-treating in substance or on thefibre with copper-yielding agents form copper complexcompounds;v v V 2.The .azodyestufis of the probable general formula: I

, (Oah f I wherein m stands for a carbon-carbon linkage or for theureabridge, 3 stands for the carboxylic acid group or for an alkoxygroup, 2 stands for the carboxylic acid group or for an alkoxy group, .Rand R stand for vbenzene radicals which'may be further substituted i by'substituents' of the group consisting of alkyl, halogen and thesulfonic acid group, the substituents .2 being attached to R or B?respectively in ortho-position to the azo-group, each azogroup beingattached to the respective hydroxy-naphthalene-sulfonic acid radical inortho-position to a hydroxy group, and n and 12' stand for the numbersone or two,

being in form of their alkali metal salts dark powders, soluble inwater, dyeing the vegetable fibre reddishto greenish-grey shades, whichby after-treating in substance or on the fibre with copper-yieldingagents form copper, complex compounds.

3. The azodyestufi of the following formula: 4

' OCH; 00in on I N=N N=N- soar:

SOaH HOaS III N OH moo being in form of its alkali metal salts a dark,watersoluble powder, dyeing cotton bluishgreenish-grey shades, which byafter-treating withcopper-sulfate become yellowishgreenish-grey.

4. The azodyestufi of the following formula:

SOsH QN==N 11 OCH; 1 moo N: I SOaH I;

being in form of its alkali metal salts a dark, watersoluble powder,dyeing cotton bluishgrey shades, which on after-treating with coppersulfate become more reddish.

5. An azodyestufi of the following forexisting in the form of its alkalimetal salts as a dark, watersoluble powder, dyeing cot ton violet-grayshades, which on after treat in with copper sulfate'become more reddish.

n testimony whereof, we aflix our signatures.

KARL WVIEDEMANN. HEINRICH CLINGESTEIN.

